Abstract:
Dispersed elements are strategic resources that play a critical role in the development of advanced and high-precision technologies. Their enrichment is commonly controlled by specific host minerals, and medium- to low-temperature hydrothermal Pb–Zn deposits are typically enriched in Cd, Ga, In, and Ge. The Taolin Pb–Zn deposit in Hunan Province is a large medium- to low-temperature hydrothermal deposit; however, the compositional characteristics and enrichment mechanisms of associated dispersed elements (Cd, Ga, In, and Ge) remain poorly constrained. In this study, detailed petrographic observations combined with in situ trace-element analyses and elemental mapping of sphalerite were conducted using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Petrographic observations indicate that sphalerite can be divided into two generations: the first-generation sphalerite is brownish yellow, whereas the second-generation sphalerite is light yellow. Analytical results show that sphalerite from the Taolin deposit is characterized by enrichment in Cd (up to 11, 734.8 ppm, with an average of 2, 978 ppm) and Ga (up to 3, 331.7 ppm, with an average of 310.7 ppm), moderate In contents (up to 322.4 ppm; average 27.1 ppm), and depletion in Ge. The Ga contents of the first-generation sphalerite are significantly higher than those of the second-generation sphalerite. Ga and In are homogeneously distributed within sphalerite, and Ga shows a strong positive correlation with Cu (R² = 0.93); similarly, Ga+In exhibits a strong positive correlation with Cu (R² = 0.92). These indicate that Ga and In are most likely incorporated into sphalerite via coupled isomorphic substitution, following the substitution mechanism Cu⁺+(Ga+In)³⁺↔2Zn²⁺. Cadmium is also homogeneously distributed within sphalerite and is inferred to occur mainly through simple isomorphic substitution (Cd²⁺↔Zn²⁺). Compared with the first-generation sphalerite, the significantly lower Ga contents in the second-generation sphalerite are interpreted to result from the involvement of late-stage meteoric water, which led to oxidation of the ore-forming fluids and conversion of Cu⁺ to Cu²⁺. The lack of low-valence cations for charge balance inhibited the incorporation of Ga³⁺ into the Zn²⁺ sites of sphalerite. The dispersed elements in sphalerite from the Taolin deposit were likely derived from late-stage magmatic–hydrothermal fluids of the Mufushan granite and metamorphic fluids released from siliceous–carbonaceous slates of the Lengjiaxi Group and Sinian strata.